技术领域technical field
本发明涉及一种基于1D金属有机框架物纳米纤维催化剂的制备方法以及基于该催化剂电解水析氧的应用，属于纳米催化、纳米材料、金属有机框架物材料技术领域。The invention relates to a preparation method of a 1D metal-organic framework nanofiber catalyst and an application of the catalyst to electrolyze water for oxygen evolution, and belongs to the technical fields of nano-catalysis, nano-materials and metal-organic framework materials.
背景技术Background technique
随着社会经济的高速发展和世界人口的不断增长，人类对化石燃料，如煤和石油等的耗用，给现有的能源储备和自然环境带来了前所未有的压力和挑战。为应对新生的能源消费以及现有人口生活质量提高的要求，世界各国均亟待寻找到可持续使用的清洁能源载体。电催化直接分解水制备氢气被认为实现该过程有效的方式。电催化分解水反应包括析氢(hydrogen evolution reaction，HER)和析氧(oxygen evolution reaction，OER)两个半反应，来自电阻、反应以及传输三个方面系统本征的能量损耗以及现有催化剂的价格、活性和稳定性方面的因素，都极大地限制了其推广和广泛应用。尽管析氧仅是一个副反应，但是为了驱动析氧反应给系统运行带来的功耗损失却最大，成为提高整体效率的瓶颈。寻找廉价易得且性能稳定的新型析氧电催化剂，对长远发展氢能、减小环境污染乃至缓解世界范围内的能源问题，具有广泛且重要的现实意义。With the rapid development of social economy and the continuous growth of the world population, human consumption of fossil fuels, such as coal and oil, has brought unprecedented pressure and challenges to the existing energy reserves and the natural environment. In order to meet the requirements of the new energy consumption and the improvement of the living quality of the existing population, all countries in the world urgently need to find sustainable and clean energy carriers. Electrocatalytic direct water splitting to produce hydrogen is considered to be an efficient way to realize this process. The electrocatalytic water splitting reaction includes two half-reactions of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which come from the inherent energy loss of the system in three aspects: resistance, reaction and transmission, and the price of existing catalysts , activity and stability factors have greatly limited its promotion and wide application. Although oxygen evolution is only a side reaction, the power consumption loss caused by driving the oxygen evolution reaction to the system operation is the largest, which becomes the bottleneck of improving the overall efficiency. Finding a new type of oxygen evolution electrocatalyst that is cheap, easy to obtain and stable in performance has extensive and important practical significance for the long-term development of hydrogen energy, the reduction of environmental pollution, and the alleviation of energy problems worldwide.
在很多已探索的体系中，二氧化铱(IrO2)和二氧化钌(RuO2)被认为最有效。然而，他们稀缺和昂贵的价格，限制了其广泛实际的应用，为此，开发高效、价廉且地球含量丰富的非贵金属析氧催化剂，降低析氧电消耗成为一个机遇和挑战。Among the many explored systems, iridium dioxide (IrO2 ) and ruthenium dioxide (RuO2 ) are considered to be the most effective. However, their scarcity and high price limit their wide practical applications. Therefore, it is an opportunity and a challenge to develop efficient, cheap and earth-abundant non-precious metal oxygen evolution catalysts to reduce the electricity consumption of oxygen evolution.
价廉的铁、钴、镍催化剂，是已报道实现高活性析氧有前景的催化剂。此外，碳基或杂原子掺杂的复合材料也是析氧催化剂的创新性选择。除了材料组成之外，催化剂的活性和其形态密切相关。为此，研究开发具有资源丰富的新组成和新形态催化剂，对实现高活性析氧具有重要的意义。Inexpensive iron, cobalt, and nickel catalysts are promising catalysts that have been reported to achieve high-activity oxygen evolution. In addition, carbon-based or heteroatom-doped composites are also innovative options for oxygen evolution catalysts. In addition to material composition, catalyst activity is closely related to its morphology. For this reason, the research and development of catalysts with new compositions and new forms with abundant resources is of great significance for the realization of highly active oxygen evolution.
作为一类新型多孔晶体材料，近年来，金属有机框架物(MOFs)在气体储存、分离、催化、识别和药物传输等领域获得了广泛的应用。MOFs周期性的多孔结构、高的比表面积以及结构的多样性，提供了以其为前体构建碳或(和)金属基纳米材料的独特优势。目前，源于MOFs前体或模板的功能材料的研究日益增多，例如，多孔碳、金属氧化物、金属/碳和金属氧化物/碳纳米材料已被报道，所构建的3D金属氧化物，用于高效超级电容器、锂离子电池和氧还原，已显现出优异的性质。2014年，Chaikittisilp和他的团队首次报道了以MOFs为前体制备电催化剂用于分解水的报道[Chaikittisilp, W., Torad, N. L., Li等，Chem.Eur. J., 2014, 20, 4217-4221]，他们采用类沸石Co-MOF (ZIF-9)为前体制备纳米多孔CoxOy-C复合材料电催化OER。因直接高温热解MOFs前体的方法常常导致框架倒塌和团聚，为此，目前常采用的一个创新性策略是利用例如石墨烯、多壁碳纳米管(multiwalled carbonnanotubes，CNTs)的纳米碳材负载MOFs，再通过高温热解制备碳基复合材料电催化剂，以阻止产物团聚并提高其比表面积。例如，2016年，Aijaz和他的团队[Aijaz, A., Masa, J., Rösler, C.等，.Angew. Chem. Int. Ed., 2016, 55, 4087-4091]将Co-MOF在H2氛中高温还原并氧化煅烧，制得了一种Co@Co3O4纳米粒子镶嵌在碳纳米管接枝的氮掺杂的碳多面体高活性析氧催化剂。虽然MOFs种类繁多，但易于制备且转变为可控形态的电催化剂MOFs前体，数量有限，目前，以三维(3D) MOFs微晶或纳米晶体为前体制备析氧催化剂的研究已有报道，据我们所知，基于一维MOFs纳米纤维制备析氧催化剂的研究未见报道。As a new class of porous crystalline materials, metal-organic frameworks (MOFs) have been widely used in gas storage, separation, catalysis, recognition, and drug delivery in recent years. The periodic porous structure, high specific surface area, and structural diversity of MOFs provide unique advantages for constructing carbon or (and) metal-based nanomaterials using them as precursors. At present, the research on functional materials derived from MOFs precursors or templates is increasing, for example, porous carbon, metal oxides, metal/carbon and metal oxide/carbon nanomaterials have been reported, and the constructed 3D metal oxides, using Excellent properties have been shown for high-efficiency supercapacitors, lithium-ion batteries, and oxygen reduction. In 2014, Chaikittisilp and his team first reported the use of MOFs as precursors to prepare electrocatalysts for water splitting [Chaikittisilp, W., Torad, NL, Li et al., Chem.Eur. J., 2014, 20, 4217 -4221], they used zeolite Co-MOF (ZIF-9) as precursor to prepare nanoporous Cox Oy -C composites for electrocatalytic OER. Because the direct high-temperature pyrolysis method of MOFs precursors often leads to frame collapse and agglomeration, an innovative strategy that is currently used is to use nano-carbon materials such as graphene and multiwalled carbon nanotubes (CNTs) to support MOFs, and then prepare carbon-based composite electrocatalysts by high-temperature pyrolysis to prevent product agglomeration and increase its specific surface area. For example, in 2016, Aijaz and his team [Aijaz, A., Masa, J., Rösler, C. et al.,. Angew. Chem. Int. Ed., 2016, 55, 4087-4091] Co-MOF in High-temperature reduction and oxidative calcination in H2 atmosphere, a nitrogen-doped carbon polyhedron with Co@Co3 O4 nanoparticles embedded in carbon nanotubes grafted with high activity oxygen evolution catalyst was prepared. Although there are many types of MOFs, the number of MOFs precursors for electrocatalysts that are easy to prepare and transform into controllable forms is limited. At present, the preparation of oxygen evolution catalysts using three-dimensional (3D) MOFs microcrystals or nanocrystals as precursors has been reported. To the best of our knowledge, the preparation of oxygen evolution catalysts based on 1D MOFs nanofibers has not been reported.
钴元素地球含量丰富，其氧化物价格低廉，然而，本体钴氧化物导电性差，其电催化析氧活性也差。本开发首先制备了Cu-MOF纳米纤维，在此基础上采用一步室温工艺，制备了负载Co2+纳米纤维CuCo-MOF，以该纳米纤维为前体，在空气中热解，制备了碳基过渡金属复合氧化物纳米纤维高效催化剂。Cobalt is abundant in the earth, and its oxides are cheap. However, bulk cobalt oxides have poor conductivity and poor electrocatalytic oxygen evolution activity. In this development, Cu-MOF nanofibers were firstly prepared. On this basis, a one-step room temperature process was adopted to prepare Co2+ -loaded nanofiber CuCo-MOF. Using the nanofiber as a precursor, it was pyrolyzed in air to prepare a carbon-based High-efficiency catalysts for transition metal composite oxide nanofibers.
发明内容Contents of the invention
本发明的技术任务之一是为了弥补现有技术的不足，提供一种基于1D金属有机框架物纳米纤维催化剂，即碳基铜钴氧化物纳米纤维催化剂的制备方法，该方法所用原料成本低，制备工艺简单，反应能耗低，具有工业应用前景。One of the technical tasks of the present invention is to provide a method for preparing a carbon-based copper-cobalt oxide nanofiber catalyst based on 1D metal-organic framework nanofiber catalysts in order to make up for the deficiencies in the prior art. The cost of raw materials used in the method is low, The preparation process is simple, the reaction energy consumption is low, and the method has industrial application prospects.
本发明的技术任务之二是提供所述碳基铜钴氧化物纳米纤维催化剂的用途，即将该碳基铜钴氧化物纳米纤维用于高效催化电解水析氧，该催化剂具有良好的析氧电催化活性与电化学稳定性。The second technical task of the present invention is to provide the use of the carbon-based copper-cobalt oxide nanofiber catalyst, that is, to use the carbon-based copper-cobalt oxide nanofiber to efficiently catalyze the electrolysis of water for oxygen evolution. Catalytic activity and electrochemical stability.
为实现上述目的，本发明采用的技术方案如下：To achieve the above object, the technical scheme adopted in the present invention is as follows:
1. 一种基于1D金属有机框架物纳米纤维催化剂的制备方法，步骤如下：1. A preparation method based on 1D metal-organic framework nanofiber catalyst, the steps are as follows:
将硝酸铜和硝酸钴共溶于15-18 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40mmol 的L-天冬氨酸与0.50-0.58 mmol氢氧化钠溶于2.0 -4.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；Co-dissolve copper nitrate and cobalt nitrate in 15-18 mL of water to obtain a blue clear copper nitrate-cobalt nitrate mixture; dissolve 0.40 mmol of L-aspartic acid and 0.50-0.58 mmol of sodium hydroxide in 2.0 - 4.0 mL of water to obtain a clear aspartic acid base solution; add the aspartic acid base solution to the copper nitrate-cobalt nitrate mixture, room temperature for 5 minutes, a precipitate is formed; after 1 hour, suction filter and dry at 60°C to obtain Cu -MOF nanofibers loaded with Co(II) ions, namely CuCo-MOF nanofibers;
将CuCo-MOF纳米纤维置于管式炉加热，制得碳基铜钴氧化物纳米纤维催化剂，即基于1D金属有机框架物纳米纤维催化剂；The CuCo-MOF nanofibers were heated in a tube furnace to prepare a carbon-based copper-cobalt oxide nanofiber catalyst, which is a 1D metal-organic framework-based nanofiber catalyst;
1）所述硝酸铜和硝酸钴，量比为4：5—1：9，总量为0.63—3.28 mmol；1) The amount ratio of copper nitrate and cobalt nitrate is 4:5-1:9, and the total amount is 0.63-3.28 mmol;
2）所述Cu-MOF纳米纤维，属金属有机框架物，化学式为[CuL(H2O)]n，L为天冬氨酸H2L的L(II) 离子；Cu-MOF纳米纤维的一个单元结构，由一个Cu(II)离子中心、一个L(II) 离子和一个H2O分子构成；2) The Cu-MOF nanofiber is a metal-organic framework, and its chemical formula is [CuL(H2 O)]n, where L is the L(II) ion of aspartic acid H2 L; the Cu-MOF nanofiber A unit structure consisting of a Cu(II) ion center, a L(II) ion and a H2 O molecule;
3）所述CuCo-MOF纳米纤维，是由Cu-MOF双纳米线以及3-10个纳米线负载Co(II) 离子沿纵向排列组成，纤维内纳米线间结合紧密，纳米线间晶界清晰可见，纤维表面沿纵向凹凸有序，凹凸尺寸不超过100 nm，纤维纵向最长可达1mm，直径宽约为80-600nm，纤维的横向裂纹也清晰可见；Cu和Co 元素均匀分布。3) The CuCo-MOF nanofiber is composed of Cu-MOF double nanowires and 3-10 nanowires loaded with Co(II) ions arranged in the longitudinal direction, the nanowires in the fiber are tightly bonded, and the grain boundaries between the nanowires are clear It can be seen that the surface of the fiber is concave and convex along the longitudinal direction, and the size of the concave and convex does not exceed 100 nm. The longest length of the fiber can reach 1 mm, and the diameter is about 80-600 nm. The transverse cracks of the fiber are also clearly visible; Cu and Co elements are evenly distributed.
所述碳基铜钴氧化物纳米纤维催化剂，纵向长度可达1mm，纤维径宽为90-120 nm；The carbon-based copper cobalt oxide nanofiber catalyst has a longitudinal length of up to 1 mm and a fiber diameter width of 90-120 nm;
4）所述基于1D金属有机框架物纳米纤维催化剂，是CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米纤维复合材料。4) The 1D metal-organic framework-based nanofiber catalyst is a nanofiber composite material composed of CuO and Co2 O3 semiconductor nanoparticles supported on carbon crystallites.
5）所述CuCo-MOF纳米纤维置于管式炉加热，是在空气氛下进行，升温速率为 3-5℃/min，加热至250-300 ℃，保温1.5-2.5 h，然后，以 2 ℃/ min 降温速率冷却到室温。5) The CuCo-MOF nanofibers were heated in a tube furnace under an air atmosphere at a heating rate of 3-5°C/min, heated to 250-300°C, kept for 1.5-2.5 h, and then, 2 °C/min cooling rate to room temperature.
2. 上述基于1D金属有机框架物的纳米纤维催化剂作为电解水析氧催化剂的应用，步骤如下：2. The above-mentioned 1D metal-organic framework-based nanofiber catalyst is used as an oxygen evolution catalyst for electrolysis of water, and the steps are as follows:
将6 mg 基于1D金属有机框架物的纳米纤维催化剂分散于250 μL乙醇、720 μL 水以及30 μL、5 wt%全氟化树脂溶液中，室温120 W至少超声10-15 min，制得均匀混合液；滴加 6μL该混合液到玻碳电极上，室温干燥，制得基于1D金属有机框架物的纳米纤维催化剂工作电极；Disperse 6 mg of 1D metal-organic framework-based nanofiber catalyst in 250 μL of ethanol, 720 μL of water, and 30 μL of 5 wt% perfluorinated resin solution, and sonicate for at least 10-15 min at room temperature at 120 W to obtain a uniform mixture solution; drop 6 μL of the mixture onto the glassy carbon electrode, and dry at room temperature to obtain a nanofiber catalyst working electrode based on a 1D metal-organic framework;
使用三电极电化学工作站，基于1D金属有机框架物的纳米纤维催化剂工作电极，Pt 片(5 mm×5 mm×0.1 mm)为对电极，Ag/AgCl电极为参比电极，在电解液为 0.5 M KOH水溶液中测试电催化分解水性能。Using a three-electrode electrochemical workstation, the nanofiber catalyst working electrode based on 1D metal organic framework, the Pt sheet (5 mm × 5 mm × 0.1 mm) as the counter electrode, the Ag/AgCl electrode as the reference electrode, and the electrolyte is 0.5 The electrocatalytic water splitting performance was tested in M KOH aqueous solution.
上述基于1D金属有机框架物的纳米纤维催化剂电解水析氧，当电流密度J=10 mA/cm2时，电位为1.53 V（vs RHE）；塔菲尔斜率为73 mV dec-1，均说明该材料高效的析氧催化活性；循环 500 次前后，该类材料极化曲线没有发现明显的变化，表明催化剂具有良好的稳定性。The above-mentioned nanofibrous catalyst based on 1D metal organic frameworks electrolyzes water for oxygen evolution. When the current density J=10 mA/cm2 , the potential is 1.53 V (vs RHE); the Tafel slope is 73 mV dec-1 , which means that The material has high oxygen evolution catalytic activity; before and after 500 cycles, the polarization curve of this type of material has no obvious change, indicating that the catalyst has good stability.
本发明的有益的技术效果：Beneficial technical effect of the present invention:
1. 本发明获得的基于1D金属有机框架物纳米纤维催化剂是由一维金属有机框架物CuCo-MOF纳米纤维，空气氛条件250-300℃加热热解生成，制备过程工艺简单，简单易控，产物制备效率高，易于工业化。1. The 1D metal-organic framework-based nanofiber catalyst obtained in the present invention is produced by one-dimensional metal-organic framework CuCo-MOF nanofibers, which are heated and pyrolyzed at 250-300°C in an air atmosphere. The preparation process is simple and easy to control. The product has high preparation efficiency and is easy to be industrialized.
2. 本发明基于1D金属有机框架物的纳米纤维，形貌规整、单一分散，比表面积高。由于该催化剂是由CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米纤维，暴露了更多且不同的活性位点，发挥了CuO、Co2O3半导体纳米粒子以及碳微晶的协同作用，使得基于该复合材料的催化析氧，催化效率高且稳定性好。2. The nanofibers based on 1D metal-organic frameworks of the present invention have regular shape, single dispersion, and high specific surface area. Since the catalyst is a nanofiber composed of CuO and Co2 O3 semiconductor nanoparticles supported on carbon microcrystals, more and different active sites are exposed, and CuO, Co2 O3 semiconductor nanoparticles and carbon microcrystals are fully utilized. The synergistic effect of crystals makes the catalytic oxygen evolution based on the composite material high in catalytic efficiency and good in stability.
具体实施方式detailed description
下面结合实施例对本发明作进一步描述，但本发明的保护范围不仅局限于实施例，该领域专业人员对本发明技术方案所作的改变，均应属于本发明的保护范围内。The present invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not only limited to embodiment, and the change that the professional of this field makes to technical solution of the present invention all should belong in protection scope of the present invention.
实施例1Example 1
1. 一种基于1D金属有机框架物纳米纤维催化剂的制备方法1. A preparation method based on 1D metal-organic framework nanofiber catalyst
将量比为4：5、总量为0.63 mmol的硝酸铜和硝酸钴共溶于15 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.50 mmol氢氧化钠溶于2.0mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；Co-dissolve copper nitrate and cobalt nitrate with a volume ratio of 4:5 and a total amount of 0.63 mmol in 15 mL of water to obtain a blue and clear copper nitrate-cobalt nitrate mixture; mix 0.40 mmol of L-aspartic acid with Dissolve 0.50 mmol of sodium hydroxide in 2.0 mL of water to obtain a clear aspartic acid base solution; add the aspartic acid base solution to the copper nitrate-cobalt nitrate mixture, and leave it at room temperature for 5 minutes to form a precipitate; after 1 hour, suction filter, Dry at 60°C to prepare Cu-MOF nanofibers loaded with Co(II) ions, namely CuCo-MOF nanofibers;
将CuCo-MOF纳米纤维置于管式炉中，在空气氛下加热，升温速率为 3-5℃/min，加热至250℃，保温1.5 h，然后，以 2℃/ min 降温速率冷却到室温，制得碳基铜钴氧化物纳米纤维催化剂，即基于1D金属有机框架物纳米纤维催化剂。Place the CuCo-MOF nanofibers in a tube furnace, heat them in an air atmosphere at a heating rate of 3-5°C/min, heat to 250°C, keep them for 1.5 h, and then cool them down to room temperature at a cooling rate of 2°C/min , to prepare a carbon-based copper-cobalt oxide nanofiber catalyst, that is, a nanofiber catalyst based on a 1D metal-organic framework.
实施例2Example 2
1. 一种基于1D金属有机框架物纳米纤维催化剂的制备方法1. A preparation method based on 1D metal-organic framework nanofiber catalyst
将量比为1：9、总量为3.28 mmol的硝酸铜和硝酸钴共溶于18 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.58 mmol氢氧化钠溶于4.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；Co-dissolve copper nitrate and cobalt nitrate with a volume ratio of 1:9 and a total amount of 3.28 mmol in 18 mL of water to obtain a blue clear copper nitrate-cobalt nitrate mixture; mix 0.40 mmol of L-aspartic acid with Dissolve 0.58 mmol of sodium hydroxide in 4.0 mL of water to obtain a clear aspartic acid base solution; add the aspartic acid base solution to the copper nitrate-cobalt nitrate mixture, and leave it at room temperature for 5 minutes to form a precipitate; Dry at 60°C to prepare Cu-MOF nanofibers loaded with Co(II) ions, namely CuCo-MOF nanofibers;
将CuCo-MOF纳米纤维置于管式炉中，在空气氛下，升温速率为 3-5℃/min，加热至300℃，保温2.5 h，然后，以 2℃/ min 降温速率冷却到室温，制得碳基铜钴氧化物纳米纤维催化剂，即基于1D金属有机框架物纳米纤维催化剂。The CuCo-MOF nanofibers were placed in a tube furnace in an air atmosphere at a heating rate of 3-5 °C/min, heated to 300 °C, kept for 2.5 h, and then cooled to room temperature at a cooling rate of 2 °C/min. A carbon-based copper-cobalt oxide nanofiber catalyst, that is, a 1D metal-organic framework-based nanofiber catalyst, is prepared.
实施例3Example 3
1. 一种基于1D金属有机框架物纳米纤维催化剂的制备方法，步骤如下：1. A preparation method based on 1D metal-organic framework nanofiber catalyst, the steps are as follows:
将量比为3：7、总量为2.0 mmol的硝酸铜和硝酸钴共溶于17 mL水，得到蓝色澄清的硝酸铜-硝酸钴混合液；将0.40 mmol 的L-天冬氨酸与0.55 mmol氢氧化钠溶于3.0 mL水，得到澄清的天冬氨酸碱溶液；将天冬氨酸碱溶液加入到硝酸铜-硝酸钴混合液中，室温5min，生成沉淀；1h后抽滤，60℃干燥，制得Cu-MOF纳米纤维负载Co(II) 离子即CuCo-MOF纳米纤维；Co-dissolve copper nitrate and cobalt nitrate with a volume ratio of 3:7 and a total amount of 2.0 mmol in 17 mL of water to obtain a blue clear copper nitrate-cobalt nitrate mixture; mix 0.40 mmol of L-aspartic acid with Dissolve 0.55 mmol of sodium hydroxide in 3.0 mL of water to obtain a clear aspartic acid base solution; add the aspartic acid base solution to the copper nitrate-cobalt nitrate mixture, and leave it at room temperature for 5 minutes to form a precipitate; Dry at 60°C to prepare Cu-MOF nanofibers loaded with Co(II) ions, namely CuCo-MOF nanofibers;
将CuCo-MOF纳米纤维置于管式炉中。在空气氛下，升温速率为 3-5℃/min，加热至270℃，保温2 h，然后，以 2℃/ min 降温速率冷却到室温，制得碳基铜钴氧化物纳米纤维催化剂，即基于1D金属有机框架物纳米纤维催化剂。The CuCo-MOF nanofibers were placed in a tube furnace. In an air atmosphere, the heating rate is 3-5 °C/min, heated to 270 °C, and kept for 2 h, and then cooled to room temperature at a cooling rate of 2 °C/min to prepare a carbon-based copper-cobalt oxide nanofiber catalyst, namely 1D metal-organic framework-based nanofibrous catalysts.
实施例4Example 4
实施例1-3所述的Cu-MOF纳米纤维，化学式为[CuL(H2O)]n，L为天冬氨酸H2L的L(II)离子；Cu-MOF纳米纤维的一个单元结构，由一个Cu(II)离子中心、一个L(II) 离子和一个H2O分子构成；Cu-MOF nanofiber described in embodiment 1-3, chemical formula is [CuL(H2 O)]n, L is the L(II) ion of aspartic acid H2 L; a unit of Cu-MOF nanofiber structure, consisting of a Cu(II) ion center, a L(II) ion and a H2 O molecule;
所述CuCo-MOF纳米纤维，是由Cu-MOF双纳米线以及3-10个纳米线负载Co(II) 离子沿纵向排列组成，纤维内纳米线间结合紧密，纳米线间晶界清晰可见，纤维表面沿纵向凹凸有序，凹凸尺寸不超过100 nm，纤维纵向最长可达1mm，直径宽约为80-600nm，纤维的横向裂纹也清晰可见；Cu和Co 元素均匀分布；The CuCo-MOF nanofiber is composed of Cu-MOF double nanowires and 3-10 nanowires loaded with Co(II) ions arranged in the longitudinal direction, the nanowires in the fiber are tightly bonded, and the grain boundaries between the nanowires are clearly visible. The surface of the fiber is uneven and orderly along the longitudinal direction, the size of the unevenness does not exceed 100 nm, the longest length of the fiber can reach 1mm, the diameter width is about 80-600nm, and the transverse cracks of the fiber are also clearly visible; Cu and Co elements are evenly distributed;
所述基于1D金属有机框架物纳米纤维催化剂，纵向长度可达1mm，纤维径宽为90-120nm，是CuO和Co2O3半导体纳米粒子负载在碳微晶上构成的纳米纤维复合材料。The 1D metal-organic framework-based nanofiber catalyst has a longitudinal length of up to 1 mm and a fiber diameter of 90-120 nm. It is a nanofiber composite material composed of CuO and Co2 O3 semiconductor nanoparticles supported on carbon crystallites.
实施例5 基于1D金属有机框架物纳米纤维催化剂作为电解水析氧催化剂的应用Example 5 Application of 1D metal-organic framework-based nanofiber catalyst as an oxygen evolution catalyst for electrolysis of water
分别称取实施例1-3制得的6mg基于1D金属有机框架物纳米纤维催化剂，分散于250μL乙醇、720μL 水以及30μL、5 wt%全氟化树脂溶液中，室温120W至少超声10-15min，制得均匀混合液；滴加 6μL该混合液到玻碳电极上，室温干燥，制得基于1D金属有机框架物纳米纤维工作电极；Weigh 6 mg of the 1D metal-organic framework nanofiber catalysts prepared in Examples 1-3, disperse them in 250 μL of ethanol, 720 μL of water, and 30 μL of 5 wt% perfluorinated resin solution, and ultrasonicate at room temperature for at least 10-15 minutes at 120 W. Prepare a uniform mixed solution; drop 6 μL of the mixed solution onto the glassy carbon electrode, and dry at room temperature to prepare a 1D metal-organic framework-based nanofiber working electrode;
使用三电极电化学工作站，基于1D金属有机框架物纳米纤维工作电极，Pt 片 (5 mm×5 mm×0.1 mm)为对电极，Ag/AgCl电极为参比电极，在电解液为 0.5 M KOH水溶液中测试电催化分解水性能；A three-electrode electrochemical workstation was used, based on 1D metal-organic framework nanofiber working electrode, Pt sheet (5 mm×5 mm×0.1 mm) as counter electrode, Ag/AgCl electrode as reference electrode, and 0.5 M KOH in electrolyte Test the performance of electrocatalytic water splitting in aqueous solution;
上述基于1D金属有机框架物纳米纤维工作电极电解水析氧，当电流密度J=10mA/cm2时，电位为1.53 V（vs RHE），塔菲尔斜率为73mV dec-1，说明该材料高效的析氧催化活性；循环 500 次前后，该类材料极化曲线没有发现明显的变化，表明催化剂具有良好的稳定性。。The above-mentioned 1D metal-organic framework nanofiber working electrode electrolyzes water for oxygen evolution. When the current density J=10mA/cm2 , the potential is 1.53 V (vs RHE), and the Tafel slope is 73mV dec-1 , indicating that the material is highly efficient. Oxygen evolution catalytic activity; before and after 500 cycles, the polarization curve of this type of material did not change significantly, indicating that the catalyst has good stability. .
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